CN113528836A - Method for separating and recovering selenium and mercury in acid mud by one-step method - Google Patents
Method for separating and recovering selenium and mercury in acid mud by one-step method Download PDFInfo
- Publication number
- CN113528836A CN113528836A CN202110837163.5A CN202110837163A CN113528836A CN 113528836 A CN113528836 A CN 113528836A CN 202110837163 A CN202110837163 A CN 202110837163A CN 113528836 A CN113528836 A CN 113528836A
- Authority
- CN
- China
- Prior art keywords
- selenium
- acid
- mercury
- seo
- crude
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 85
- 239000011669 selenium Substances 0.000 title claims abstract description 85
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 69
- 239000002253 acid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 238000010521 absorption reaction Methods 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 239000010802 sludge Substances 0.000 claims abstract description 26
- 239000002893 slag Substances 0.000 claims abstract description 24
- 229910018162 SeO2 Inorganic materials 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910003597 H2SeO3 Inorganic materials 0.000 claims abstract description 12
- 239000003546 flue gas Substances 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/004—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B43/00—Obtaining mercury
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for separating and recovering selenium and mercury in acid sludge by a one-step method, belonging to the technical field of acid sludge treatment. Mixing acid mud and slurrying liquid, and slurrying for 30-120 min to obtain a slurry; wherein the slurry liquid contains acid liquid and oxidant; placing the slurry at the temperature of 400-800 ℃ for microwave roasting for 20-120 min to obtain Hg and SeO2The mixed steam and the roasting slag, and valuable metal recovery is carried out on the roasting slag; hg and SeO2The mixed vapor is condensed and separated to obtain SeO2Crude vapor and elemental Hg; SeO2Introducing the crude steam into an absorption tower for hydrolysis to obtain H2SeO3Introduction of SO2Reduction of flue gas to H2SeO3Obtaining crude selenium, drying the crude selenium, and refining to obtain refined selenium. The invention directly bakes the selenium and mercury phases in the acid mud into SeO2And mercury is condensed and recovered, selenium dioxide is reduced and recovered, and is refined, and the mercury-containing slag and the selenium-containing slag generated in the process are refined again, so that the harmful acid sludge is efficiently and simply treated.
Description
Technical Field
The invention relates to a method for separating and recovering selenium and mercury in acid sludge by a one-step method, belonging to the technical field of acid sludge treatment.
Background
The treatment of mercury and selenium pollution has become one of the main concerns in the field of global environmental science and technology. The deep treatment of valuable smelting resources containing mercury and selenium becomes a challenge in the field of mercury pollution treatment, and research and development of the method for efficiently removing mercury and selenium in the valuable smelting resources becomes an urgent need for guaranteeing the safety of ecological environment.
In the prior art, the method for separating selenium, mercury and lead from acid mud by chlorination leaching comprises the steps of firstly adding sodium chlorate to leach mercury and selenium by oxidation, and then introducing SO2Crude selenium is reduced, sodium sulfide is added to precipitate mercury, selenium, mercury and lead can be separated and recovered cleanly and efficiently, the comprehensive recovery rate of metal is improved, and environmental pollution is reduced; the invention relates to a method for comprehensively recovering selenium, mercury, lead and silver from acid sludge, which comprises the steps of adding dilute acid to selectively leach lead in conversion slag, adding sodium chloride to deposit silver, adding an oxidant and acid to chloridize and leach selenium and mercury to separate silver, reducing crude selenium by sulfur dioxide, and adding a vulcanizing agent to deposit mercury, wherein the method is a full-wet method for treating and smelting acid sludge, and is low in temperature, environment-friendly, the mercury yield of the full process is more than 99.5%, the lead content is more than 95.0%, and the selenium content is more than 98.0%; the method for separating mercury, selenium and lead from nonferrous smelting acid sludge comprises the steps of pressurizing, oxidizing and leaching mercury and lead, synthesizing copper amalgam by copper scrap displacement, and adding alkali into lead-containing liquid to precipitate lead.
However, in the prior art, the mercury is precipitated by using a wet process, and the sodium sulfide is added to generate the mercury sulfide, so that the added value of the product is low.
Disclosure of Invention
Aiming at the problems of complex technical process for treating the acid sludge, difficult separation of selenium and mercury and the like in the prior art, the invention provides a method for separating and recovering selenium and mercury in the acid sludge by one step, namely directly roasting selenium and mercury phases in the acid sludge to form SeO2Mercury is condensed and recovered, selenium dioxide is reduced and recovered, and refined, and the mercury-containing slag and selenium-containing slag generated in the process are refined again, so that the high-efficiency and simple operation of harmful acid sludge is realizedAnd (5) single processing.
A method for separating and recovering selenium and mercury in acid sludge by a one-step method comprises the following specific steps:
(1) mixing the acid mud and the slurrying liquid for slurrying for 30-120 min to obtain a slurried substance; wherein the slurry liquid contains acid liquid and oxidant;
(2) placing the slurry obtained in the step (1) at the temperature of 400-800 ℃ for microwave roasting for 20-120 min to obtain Hg and SeO2The roasting slag is subjected to pyrometallurgical valuable metal recovery;
(3) hg and SeO of step (2)2The mixed vapor is condensed and separated to obtain SeO2Crude vapor and elemental Hg;
(4) step (3) SeO2Introducing the crude steam into an absorption tower, and hydrolyzing at the temperature of 60-95 ℃ to obtain H2SeO3Introduction of SO2Reduction of flue gas to H2SeO3And adding lead sheets into the absorption tower liquid, carrying out reduction and replacement at the temperature of 60-95 ℃ to obtain crude selenium II and a reduced liquid, and mixing and drying the crude selenium I and the crude selenium II and then refining to obtain refined selenium.
In the acid mud obtained in the step (1), the mass content of mercury is 1-43%, and the mass content of selenium is 1-71%; the acid solution is sulfuric acid, hydrochloric acid or nitric acid, the oxidant is potassium permanganate, manganese dioxide, hydrogen peroxide or hypochlorous acid, and the slurrying temperature is 25-90 ℃;
the acid concentration in the slurry is 20-200 g/L, and the oxidant concentration in the slurry is 2-100 g/L, namely 0.1-5% of the mass of the acid mud;
the microwave roasting atmosphere in the step (2) is air or oxygen atmosphere, and the introduction flow of the air or the oxygen is 1-20L/min;
the condensation temperature in the step (3) is 20-75 ℃;
the water amount in the absorption tower in the step (4) accounts for 10-70% of the volume of the absorption tower, and the acid concentration in the liquid of the absorption tower is 100-500 g/L;
the drying temperature in the step (4) is 120-140 ℃.
The invention has the beneficial effects that:
(1) the method has the advantages that the selenium and the mercury are separated by the one-step method, the mercury is separated by the elemental mercury, the selenium is separated by the selenium dioxide, the separation efficiency is high, and the separation of the selenium and the mercury can reach more than 99 percent;
(2) the method has the advantages of short mercury separation flow, closed process and no mercury leakage;
(3) the lead-containing slag after the selenium and mercury are extracted can be directly returned to the system, and the safety and the controllability are high.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is the XRD pattern of the acid mud material of example 1;
FIG. 3 is the XRD pattern of the roasted slag after the acid sludge is subjected to selenium and mercury removal in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the method for separating and recovering selenium and mercury in acid sludge by one-step process (see figure 1) comprises the following steps:
(1) slurrying: mixing the acid mud with the slurry, and slurrying at 25 deg.C for 120min to obtain slurry; wherein the mercury content in the dried acid mud is 1% by mass, the selenium content is 1% by mass, the solid-to-liquid ratio g: mL of the acid mud to the slurry liquid is 1:6, the slurry liquid contains hydrochloric acid and an oxidant (potassium permanganate), the concentration of the hydrochloric acid in the slurry liquid is 20g/L, and the concentration of the oxidant in the slurry liquid is 2 g/L;
(2) roasting: placing the slurry obtained in the step (1) at the temperature of 400 ℃ and roasting the slurry in the air atmosphere for 20min to obtain Hg and SeO2The total content of mercury and selenium in the roasting slag is not more than 1 percent, and the roasting slag is used for recovering valuable metals by pyrometallurgy; wherein the flow rate of the air is 1L/min;
(3) condensing and recovering mercury: hg and SeO of step (2)2The mixed steam is condensed and separated into SeO by a water cooling tank with the temperature of 20 DEG C2Crude steam and Hg simple substance, the water cooling tank is composed of a water cooling circulation system and a mercury recycling tank;
(4) absorption and reduction: step (3) SeO2The crude vapor is introduced into an absorption tower, the water content in the absorption tower is 10 percent of the volume of the absorption tower, and the crude vapor is introduced into a vapor-liquid separatorSeO at a temperature of 60 DEG C2Hydrolysis to give H2SeO3Introduction of SO2Reduction of flue gas to H2SeO3Obtaining crude selenium I and absorption tower liquid, SO2The flow of flue gas does not need to be controlled, the flue gas can be absorbed at the tail gas end of the absorption tower, and the tower liquid after absorption contains about 100g/L of acid; the absorbed tower liquid enters a reduction tank, lead sheets are added into the absorption tower liquid, reduction and replacement are carried out at the temperature of 60 ℃ until the absorption tower liquid is colorless after thiourea detection to obtain crude selenium II and reduced liquid, and the crude selenium I and the crude selenium II are combined and then placed at the temperature of 120 ℃ for drying and then refined to obtain refined selenium; wherein the refining is performed by a liquation furnace or a vacuum furnace, and the selenium slag is returned to the step (2) for roasting;
in the embodiment, the XRD pattern of the acid sludge raw material is shown as 2, the XRD pattern of the roasting residue after the acid sludge is subjected to selenium and mercury removal is shown as 3, and the comparison between the figures 2 and 3 shows that the phase containing selenium and mercury after roasting treatment is completely disappeared, and only PbSO is left4Namely, the acid sludge realizes safe treatment, and the roasted lead slag can be returned to the Isa furnace for lead smelting;
in the embodiment, the recovery rate of mercury is 99%, the recovery rate of selenium is 99%, and the total content of mercury and selenium in the roasting slag after removing mercury and selenium is 0.02%.
Example 2: the method for separating and recovering selenium and mercury in acid sludge by one-step process (see figure 1) comprises the following steps:
(1) slurrying: mixing the acid mud with the slurry, and slurrying at 60 deg.C for 60min to obtain slurry; wherein the mass content of mercury in the dried acid mud is 43%, the mass content of selenium is 8%, the solid-to-liquid ratio g: mL of the acid mud to the slurry is 2:1, the slurry contains sulfuric acid and an oxidant (hydrogen peroxide), the concentration of the sulfuric acid in the slurry is 90g/L, and the concentration of the oxidant in the slurry is 35 g/L;
(2) roasting: placing the slurry obtained in the step (1) at the temperature of 600 ℃ and roasting the slurry in the air atmosphere for 60min to obtain Hg and SeO2The total content of mercury and selenium in the roasting slag is not more than 1 percent, and the roasting slag is used for recovering valuable metals by pyrometallurgy; wherein the flow rate of the air is 10L/min;
(3) condensing and recovering mercury: hg and SeO of step (2)2The mixed vapor is condensed by a water-cooling tank with the temperature of 60 ℃ to separate SeO2Crude steam and Hg simple substance, the water cooling tank is composed of a water cooling circulation system and a mercury recycling tank;
(4) absorption and reduction: step (3) SeO2Introducing the crude vapor into an absorption tower containing 50% of water at 80 deg.C, and SeO2Hydrolysis to give H2SeO3Introduction of SO2Reduction of flue gas to H2SeO3Obtaining crude selenium I and absorption tower liquid, SO2The flow of flue gas does not need to be controlled, the flue gas can be absorbed at the tail gas end of the absorption tower, and the tower liquid after absorption contains about 300g/L of acid; the absorbed tower liquid enters a reduction tank, lead sheets are added into the absorption tower liquid, reduction and replacement are carried out at the temperature of 70 ℃ until the absorption tower liquid is colorless after thiourea test to obtain crude selenium II and reduced liquid, and the crude selenium I and the crude selenium II are combined and then placed at the temperature of 130 ℃ for drying and then refined to obtain refined selenium; wherein the refining is performed by a liquation furnace or a vacuum furnace, and the selenium slag is returned to the step (2) for roasting;
in the embodiment, the recovery rate of mercury is 99.5%, the recovery rate of selenium is 99%, and the total content of mercury and selenium in the roasting slag after removing mercury and selenium is 0.5%.
Example 3: the method for separating and recovering selenium and mercury in acid sludge by one-step process (see figure 1) comprises the following steps:
(1) slurrying: mixing the acid mud with the slurry, and slurrying at 90 ℃ for 100min to obtain a slurry; wherein the mass content of mercury in the dried acid mud is 9%, the mass content of selenium is 71%, the solid-to-liquid ratio g: mL of the acid mud to the slurry liquid is 6:1, the slurry liquid contains nitric acid and an oxidant (hypochlorous acid), the concentration of the nitric acid in the slurry liquid is 200g/L, and the concentration of the oxidant in the slurry liquid is 100 g/L;
(2) roasting: placing the slurry obtained in the step (1) at the temperature of 800 ℃ and in the air atmosphere for microwave roasting for 120min to obtain Hg and SeO2The total content of mercury and selenium in the roasting slag is not more than 1 percent, and the roasting slag is used for recovering valuable metals by pyrometallurgy; wherein the flow rate of the air is 10L/min;
(3) condensing and recovering mercury: hg and SeO of step (2)2The mixed steam is condensed by a water-cooling tank with the temperature of 75 ℃ to separate out SeO2Crude steam and Hg simple substance are cooled in a water tankA water-cooling circulation system and a mercury recovery tank;
(4) absorption and reduction: step (3) SeO2Introducing the crude vapor into an absorption tower, wherein the water content in the absorption tower is 70% of the volume of the absorption tower, and the SeO is carried out at the temperature of 95 DEG C2Hydrolysis to give H2SeO3Introduction of SO2Reduction of flue gas to H2SeO3Obtaining crude selenium I and absorption tower liquid, SO2The flow of flue gas does not need to be controlled, the flue gas can be absorbed at the tail gas end of the absorption tower, and the tower liquid after absorption contains about 500g/L acid; the absorbed tower liquid enters a reduction tank, lead sheets are added into the absorption tower liquid, reduction and replacement are carried out at the temperature of 80 ℃ until the absorption tower liquid is colorless after thiourea test to obtain crude selenium II and reduced liquid, and the crude selenium I and the crude selenium II are combined and then placed at the temperature of 140 ℃ for drying and then refined to obtain refined selenium; wherein the refining is performed by a liquation furnace or a vacuum furnace, and the selenium slag is returned to the step (2) for roasting;
in the embodiment, the recovery rate of mercury is 99.9%, the recovery rate of selenium is 99.72%, and the total content of mercury and selenium in the roasting slag after removing mercury and selenium is 0.3%.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (6)
1. A method for separating and recovering selenium and mercury in acid sludge by a one-step method is characterized by comprising the following steps:
(1) mixing the acid mud and the slurrying liquid for slurrying for 30-120 min to obtain a slurried substance; wherein the slurry liquid contains acid liquid and oxidant;
(2) placing the slurry obtained in the step (1) at the temperature of 400-800 ℃ for microwave roasting for 20-120 min to obtain Hg and SeO2The roasting slag is subjected to pyrometallurgical valuable metal recovery;
(3) hg and SeO of step (2)2The mixed vapor is condensed and separated to obtain SeO2Crude vapor and elemental Hg;
(4) step (3) SeO2Crude steam introductionHydrolyzing in an absorption tower at the temperature of 60-95 ℃ to obtain H2SeO3Introduction of SO2Reduction of flue gas to H2SeO3And adding lead sheets into the absorption tower liquid, carrying out reduction and replacement at the temperature of 60-95 ℃ to obtain crude selenium II and a reduced liquid, and mixing and drying the crude selenium I and the crude selenium II and then refining to obtain refined selenium.
2. The one-step method for separating and recovering selenium and mercury from acid sludge according to claim 1, characterized in that: in the step (1), the mass content of mercury in the acid mud is 1-43%, and the mass content of selenium is 1-71%; the acid solution is sulfuric acid, hydrochloric acid or nitric acid, the oxidant is potassium permanganate, manganese dioxide, hydrogen peroxide or hypochlorous acid, and the slurrying temperature is 25-90 ℃.
3. The one-step method for separating and recovering selenium and mercury in acid sludge according to claim 1 or 2 is characterized in that: the acid concentration in the slurry is 20-200 g/L, and the oxidant concentration in the slurry is 2-100 g/L.
4. The one-step method for separating and recovering selenium and mercury from acid sludge according to claim 1, characterized in that: and (3) the microwave roasting atmosphere in the step (2) is air or oxygen atmosphere.
5. The one-step method for separating and recovering selenium and mercury from acid sludge according to claim 1, characterized in that: the condensation temperature in the step (3) is 20-75 ℃.
6. The one-step method for separating and recovering selenium and mercury from acid sludge according to claim 1, characterized in that: and (4) the water amount in the absorption tower accounts for 10-70% of the volume of the absorption tower, and the acid concentration in the liquid of the absorption tower is 100-500 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110837163.5A CN113528836B (en) | 2021-07-23 | 2021-07-23 | Method for separating and recovering selenium and mercury in acid mud by one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110837163.5A CN113528836B (en) | 2021-07-23 | 2021-07-23 | Method for separating and recovering selenium and mercury in acid mud by one-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113528836A true CN113528836A (en) | 2021-10-22 |
| CN113528836B CN113528836B (en) | 2022-07-29 |
Family
ID=78088876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110837163.5A Active CN113528836B (en) | 2021-07-23 | 2021-07-23 | Method for separating and recovering selenium and mercury in acid mud by one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113528836B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114622097A (en) * | 2022-03-18 | 2022-06-14 | 昆明理工大学 | Acid sludge value-increasing treatment method |
| CN115537550A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for efficiently separating and recovering mercury and selenium in acid mud through microwave heating and alkaline oxidation |
| CN115595433A (en) * | 2022-11-30 | 2023-01-13 | 昆明理工大学（Cn） | System for extracting valuable metals from acid mud by microwave with high selectivity |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4817690B1 (en) * | 1969-11-10 | 1973-05-31 | ||
| GB1449704A (en) * | 1973-02-16 | 1976-09-15 | Outokumpu Oy | Method for separate recovery of selenium and mercury from raw materials containing them |
| US5478540A (en) * | 1994-04-22 | 1995-12-26 | Walles; Wilhelm E. | Removal of mercury heavy metal values employing sulfur trioxide |
| RU2425160C1 (en) * | 2010-06-21 | 2011-07-27 | Закрытое акционерное общество Научно-производственное предприятие "Кубаньцветмет" (ЗАО НПП "Кубаньцветмет") | Procedure for extraction of mercury out of mercury-selenium final tailings |
| CN106893865A (en) * | 2017-04-01 | 2017-06-27 | 湖南省环境保护科学研究院 | The method that mercury is extracted from weight acid mud is related to |
| CN108220606A (en) * | 2018-02-07 | 2018-06-29 | 云南省固体废物管理中心 | A kind of method of lead, mercury, selenium synthetical recovery in Copper making acid mud |
| CN109097605A (en) * | 2018-09-03 | 2018-12-28 | 昆明理工大学 | A kind of method of mercury in efficient cryogenic recovery acid mud |
| CN111057852A (en) * | 2019-12-04 | 2020-04-24 | 昆明理工大学 | Method for synchronously recycling selenium and mercury by treating acid sludge at low temperature through microwaves |
| CN112522518A (en) * | 2020-12-01 | 2021-03-19 | 昆明理工大学 | Safe control and comprehensive recycling method for high-lead mercury-containing acid mud |
| CN113088694A (en) * | 2021-03-08 | 2021-07-09 | 云南驰宏锌锗股份有限公司 | Comprehensive recovery method for valuable metals in lead-zinc smelting acid mud |
-
2021
- 2021-07-23 CN CN202110837163.5A patent/CN113528836B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4817690B1 (en) * | 1969-11-10 | 1973-05-31 | ||
| GB1449704A (en) * | 1973-02-16 | 1976-09-15 | Outokumpu Oy | Method for separate recovery of selenium and mercury from raw materials containing them |
| US5478540A (en) * | 1994-04-22 | 1995-12-26 | Walles; Wilhelm E. | Removal of mercury heavy metal values employing sulfur trioxide |
| RU2425160C1 (en) * | 2010-06-21 | 2011-07-27 | Закрытое акционерное общество Научно-производственное предприятие "Кубаньцветмет" (ЗАО НПП "Кубаньцветмет") | Procedure for extraction of mercury out of mercury-selenium final tailings |
| CN106893865A (en) * | 2017-04-01 | 2017-06-27 | 湖南省环境保护科学研究院 | The method that mercury is extracted from weight acid mud is related to |
| CN108220606A (en) * | 2018-02-07 | 2018-06-29 | 云南省固体废物管理中心 | A kind of method of lead, mercury, selenium synthetical recovery in Copper making acid mud |
| CN109097605A (en) * | 2018-09-03 | 2018-12-28 | 昆明理工大学 | A kind of method of mercury in efficient cryogenic recovery acid mud |
| CN111057852A (en) * | 2019-12-04 | 2020-04-24 | 昆明理工大学 | Method for synchronously recycling selenium and mercury by treating acid sludge at low temperature through microwaves |
| CN112522518A (en) * | 2020-12-01 | 2021-03-19 | 昆明理工大学 | Safe control and comprehensive recycling method for high-lead mercury-containing acid mud |
| CN113088694A (en) * | 2021-03-08 | 2021-07-09 | 云南驰宏锌锗股份有限公司 | Comprehensive recovery method for valuable metals in lead-zinc smelting acid mud |
Non-Patent Citations (3)
| Title |
|---|
| 何裕标: "《有色金属4》", 31 May 1966 * |
| 彭天照等: "硒分离提取技术及其研究现状", 《稀有金属与硬质合金》 * |
| 江开忠等: "火法炼汞过程中硒的行为及其综合回收", 《稀有金属》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114622097A (en) * | 2022-03-18 | 2022-06-14 | 昆明理工大学 | Acid sludge value-increasing treatment method |
| CN115537550A (en) * | 2022-11-29 | 2022-12-30 | 昆明理工大学 | Method for efficiently separating and recovering mercury and selenium in acid mud through microwave heating and alkaline oxidation |
| CN115595433A (en) * | 2022-11-30 | 2023-01-13 | 昆明理工大学（Cn） | System for extracting valuable metals from acid mud by microwave with high selectivity |
| CN115595433B (en) * | 2022-11-30 | 2023-02-28 | 昆明理工大学 | System for extracting valuable metals from acid mud with high selectivity by microwaves |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113528836B (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113528836B (en) | Method for separating and recovering selenium and mercury in acid mud by one-step method | |
| CN111996383B (en) | Method for separating arsenic from copper slag by matching high-arsenic materials | |
| AU2002349233B2 (en) | Process for the treatment of molybdenum concentrate also containing copper | |
| CN111926187A (en) | Method for comprehensively recovering selenium, mercury, lead and silver from acid sludge | |
| AU2015240414A1 (en) | Purification of copper concentrate by removal of arsenic and antimony with concomitant regeneration and recycle of lixiviant | |
| CN106756038A (en) | A kind of method that selenium mercury is separated in the acid mud from copper-lead-zinc smelting sulfate system | |
| CN115818586B (en) | Method for extracting selenium and mercury by cooperatively treating mercury selenate mud and neutralization slag | |
| CN102363842A (en) | Process for recovering arsenic comprehensively by two-section roasting of arsenic-containing and carbon-containing gold concentrates | |
| CN112458318A (en) | Recovery processing method of selenium-containing mercury acid mud | |
| CN111304447A (en) | Method and equipment for recovering arsenic from titanium arsenic slag | |
| JP3069520B2 (en) | Method for separating arsenic from smelting intermediates containing arsenic sulfide | |
| CN115011804B (en) | Air and water vapor synergistic roasting dearsenification method for high-arsenic antimony lead anode slime | |
| AU2018382228A1 (en) | Improved zinc oxide process | |
| CA2421722C (en) | Pressure leaching process for zinc recovery from sulphidic ore materials | |
| CN104862487A (en) | High-efficiency resource transformation method of nonferrous metal zinc-smelting fly ash | |
| CN108179290A (en) | A kind of method that mercury is enriched with from sour mud | |
| CN114737059A (en) | Method for treating cyaniding tailings by adopting oxygen-free roasting-persulfate leaching combined technology | |
| CN106906363A (en) | A kind of processing method containing arsenical copper slag | |
| CN113528846A (en) | Treatment method for resource utilization of arsenic-containing waste residues | |
| CN103131864A (en) | Method for pre-treating complex indium-containing smoke dust by microwave roasting | |
| AU2001287468A1 (en) | Pressure leaching process for zinc recovery from sulphidic ore materials | |
| CN113774224B (en) | Method for ultrasonically enhancing mercury-containing phase-oriented transformation in acid mud | |
| CN115724412B (en) | Method for recycling selenium-containing lead sludge | |
| CN114752754B (en) | Method for removing arsenic from black copper mud | |
| CN217732945U (en) | System for recovering mercury and selenium in colored smelting flue gas purification acid sludge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |